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Atom-efficient electrophilic aromatic nitration by dinitrogen pentoxide catalysed by zirconium(IV) 2,4-pentanedionate.
Hill, Adrian J; Millar, Ross W; Sandall, John P B.
Afiliación
  • Hill AJ; Department of Chemistry, University of Exeter, Stocker Road, Exeter, UKEX4 4QD.
Org Biomol Chem ; 2(1): 90-2, 2004 Jan 07.
Article en En | MEDLINE | ID: mdl-14737664
An atom-efficient, non-acidic, catalytic process is described for the nitration of electron deficient arenes such as o-nitrotoluene using a dinitrogen pentoxide-zirconium(iv) 2,4-pentanedionate system in dichloromethane solvent. Kinetic studies showed the nitration process to be first-order with respect to the aromatic substrate and higher than first-order with respect to the catalyst. Addition of the catalyst at ca. 0.1-1 mol% compared with both N(2)O(5) and the organic substrate results in an increase in the first-order rate constant for nitration by a factor of approximately 5000 with a turnover number of at least 500. The orientation of the nitration products (2,4-/2,6-dinitrotoluenes) is consistent with attack of nitronium ion. The apparently high order of reaction with respect to the catalyst suggests a possible heterogeneous process.
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Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Org Biomol Chem Asunto de la revista: BIOQUIMICA / QUIMICA Año: 2004 Tipo del documento: Article Pais de publicación: Reino Unido
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Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Org Biomol Chem Asunto de la revista: BIOQUIMICA / QUIMICA Año: 2004 Tipo del documento: Article Pais de publicación: Reino Unido